Cationic polymers as antistatic additives for hair preparations

ABSTRACT

An aqueous hair-treatment preparation containing an antistatic additive imparting an antistatic effect to the hair, characterized in that said antistatic additive is at least one cationic polymer produced by the process of (1) epoxidizing 1,3-diene homopolymers or copolymers, (2) amine reacting the epoxide compound so produced with low molecular weight amines selected from the group consisting of primary amines, secondary amines and tertiary amines, and (3) converting the reaction products into the salt form or into polymeric quaternary ammonium salts. The use of these polymeric amine salts or quaternary ammonium salts in cosmetic hair-treatment preparations provides these preparations with antistatic effects. Preferred cationic polymers are obtained by the expoxidation of polybutadiene, of which more than 50% of the monomer units show the 1,4-cis- configuration, reaction with dimethylamine or morpholine and conversion into the hydrochlorides or alkylation with glycidyl trimethylammonium chloride, 3-chloro-2-hydroxypropyl trimethylammonium chloride or ethylene oxide. The cationic polymers are preferably used in shampoos in quantities of from 0.5 to 5.0% by weight in addition to 5 to 30% by weight of alkylether sulfate tensides and 1 to 5% by weight of a zwitterionic or amphoteric washing-active substance.

This application is a continuation of application Ser. No. 667,383,filed Nov. 1, 1984, now abandoned which is a continuation of Ser. No.525,972 filed Aug. 24, 1983, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to cosmetic hair-treatment preparationscontaining an antistatic additive imparting an antistatic effect to thehair.

After washing with shampoos, shower and bath preparations based onsynthetic tensides, but above all after cosmetic treatments, such asdyeing and shaping, hair is often in a cosmetically unsatisfactorystate. It is difficult to comb when wet and has little hold and bodyafter drying. Above all, it tends to become statically charged whichcauses freshly washed hair to "fly".

It is known that conditioning preparations can be applied to hair afterwashing, dyeing or permanent waving. Conditioning preparations generallycontain cationic surface-active compounds as their active ingredients.It is also known that certain substances may be added to normal shampoosbased on anion-active tensides or on mixtures of tensides of differentionogenity in order to obtain a certain conditioning effect when thehair is washed. Examples of substances of the type in question arewater-soluble proteins or protein degradation products, polycationicpolymers, such as for example the synthetic polymers containingquaternary ammonium groups described in German published patentapplication No. 21 09 081 (and equivalent Canadian patent No. 958,644)or the cellulose ethers containing quaternary nitrogen which are knownfrom German published patent application No. 24 23 833 (and equivalentCanadian patent No. 1,022,075).

However, known conditioning agents have considerable drawbacks. Althoughcationic tensides are highly effective in nonionic formulations, theycan only be used in ineffective quantities, if at all, in shampoos or,for example, hair dyes containing anionic tensides on account of theirlimited compatibility with anionic tensides. In addition, anionictenside complex with quaternary ammonium compounds make the hair very"heavy", which is reflected in a greasy appearance and lack of body ofthe treated hair.

This "heaviness" is also observed to a greater or lesser extent in thecase of known, cation-active formulations for the after treatment ofhair.

Although polycationic polymers bring about a satisfactory improvement inwet compatibility, they do not effectively reduce the tendency of dryhair towards static charging. In many cases, particularly in anionic oranionic-amphoteric shampoo formulations, cationic polymers can even leadto an increase in the static chargeability of dry hair.

OBJECTS OF THE INVENTION

An object of the invention is to obtain a cosmetic hair-treatmentpreparation containing an antistatic additive imparting an antistaticeffect to the hair.

Another object of the invention is the development of an aqueoushair-treatment preparation containing an antistatic additive impartingan antistatic effect to the hair, characterized in that said antistaticadditive is at least one cationic polymer obtainable by the processcomprising

(1) epoxidizing 1,3-diene homopolymer or copolymers containing at least10 1,3-diene units up to a conversion of at least 10% of the doublebonds present,

(2) reacting the epoxidized poly-1,3-dienes with amines having theformula R¹ NR₂ R₃, in which R¹ is a member selected from the groupconsisting of hydrogen, lower alkyl containing from 1 to 4 carbon atomsand hydroxyalkyl containing from 2 to 4 carbon atoms, and R² and R³ aremembers selected from the group consisting of hydrogen, lower alkylcontaining from 1 to 4 carbon atoms, and hydroxyalkyl containing from 2to 4 carbon atoms, and together with the nitrogen atom, morpholino,piperidino and piperazino, with the proviso that at least one of R¹, R²and R³ is other than hydrogen,

(3) converting the reaction products with mineral acids or lowermolecular weight carboxylic acids into the salt form, preferably intothe hydrochlorides, or converting the polymeric tertiary amines intoquaternary ammonium salts by alkylation with compounds selected from thegroup consisting of 3-chloro-2-hydroxypropyl trimethylammonium chloride,RCl, RBr, R₂ SO₄, in which R represents methyl or ethyl or by theaddition of ethylene oxide, propylene oxide, glycidol or glycidyltrimethylammonium chloride and conversion into the salt form, preferablyinto the hydrochlorides.

A further object of the present invention is the development of anaqueous hair-treatment composition comprising at least onehair-treatment agent and an additive to impart an antistatic effect tothe hair, wherein said hair-treatment composition contains an amountsufficient to impart an antistatic effect to the hair of at least onecationic polymer produced by the process comprising

(1) epoxidizing an unsaturated polymer selected from the groupconsisting of 1,3-diene homopolymers and copolymers from 1,3-dienemonomers, said unsaturated polymer containing at least 10 1,3-dieneunits up to a conversion of at least 10% of the double bonds present,

(2) reacting the epoxidized unsaturated polymer with amines having theformula R¹ NR² R³, in which R¹ is a member selected from the groupconsisting of hydrogen, lower alkyl group containing from 1 to 4 carbonatoms and hydroxy-alkyl containing 2 to 4 carbon atoms and R² and R³ aremembers selected from the group consisting of hydrogen, lower alkylcontaining from 1 to 4 carbon atoms, hydroxyalkyl containing from 2 to 4carbon atoms and together with the nitrogen atom, morpholino, piperidinoand piperazino, with the provisio that at least one of R¹, R² and R³ isother than hydrogen,

(3) converting the aminated polymer to the salt form by a processselected from the group consisting of (a) acidifying with an acidselected from the group consisting of mineral acids andlow-molecular-weight carboxylic acids having from 1 to 7 carbon atoms,(b) quaternizing the tertiary aminated polymer by reaction with aquaternizing compound selected from the group consisting of3-chloro-2-hydroxypropyl trimethyl ammonium chloride, RCl, RBr and R₂SO₄, wherein R is member selected from the group consisting of methyland ethyl and (c) quaternizing the tertiary aminated polymer by reactionwith a quaternizing compound selected from the group consisting ofethylene oxide, propylene oxide, glycidol and glycidyl trimethylammonium chloride followed by acidifying with said acid of (a) above.

A yet further object of the present invention is the development of aprocess for imparting an antistatic effect to hair which comprisesapplying to hair the above aqueous hair-treatment composition.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

DESCRIPTION OF THE INVENTION

Accordingly, there was a need to find conditioning agents which aresuitable for use as conditioning and antistatically active additives forhair treatment preparations and which are attended by theabove-mentioned disadvantages to a far lesser extent, if at all.

The present invention relates to the use of cationic polymers obtainableby

(1) epoxidizing 1,3-diene homopolymer or copolymers containing at least10 1,3-diene units to a conversion of at least 10% of the double bondspresent,

(2) reacting the epoxidized poly-1,3-dienes with amines having theformula in which R¹ NR² R³, is a member selected from the groupconsisting of hydrogen, lower alkyl containing from 1 to 4 carbon atomsand hydroxyalkyl containing from 2 to 4 carbon atoms, and R² and R³ aremembers selected from the group consisting of hydrogen, lower alkylcontaining from 1 to 4 carbon atoms, and hydroxyalkyl containing from 2to 4 carbon atoms, and together with the nitrogen atom, morpholino,piperidino and piperazino, with the proviso that at least one of R¹, R²and R³ is other than hydrogen,

(3) converting the reaction products with mineral acids or lowermolecular weight carboxylic acids into the salt form, preferably intothe hydrochlorides, or converting the polymeric tertiary amines intoquaternary ammonium salts by alkylation with compounds selected from thegroup consisting of 3-chloro-2-hydroxypropyl trimethyl ammoniumchloride, RCl, RBr, R₂ SO₄, in which R is methyl or ethyl, or by theaddition of theylene oxide, propylene oxide, glycidol or glycidyltrimethyl ammonium chloride and conversion into the salt form,preferably into the hydrochlorides, as an antistatically active additivein cosmetic hair-treatment preparations.

More particularly, the present invention relates to an aqueoushair-treatment composition comprising at least one hair-treatment agentand an additive to impart an antistatic effect to the hair, wherein saidhair-treatment composition contains an amount sufficient to impart anantistatic effect to the hair of at least one cationic polymer producedby the process comprising

(1) epoxidizing an unsaturated polymer selected from the groupconsisting of 1,3-diene homopolymer and copolymers from 1,3-dienemonomers, said unsaturated polymer containing at least 10 1,3-dieneunits to a conversion of at least 10% of the double bond present,

(2) reacting the epoxidized unsaturated polymer with amines having theformula R¹ NR² R³, in which R¹ is a member selected from the groupconsisting of hydrogen, lower alkyl containing from 1 to 4 carbon atomsand hydroxyalkyl containing from 2 to 4 carbon atoms and R² and R³ aremembers selected from the group consisting of hydrogen, lower alkylcontaining from 1 to 4 carbon atoms, hydroxyalkyl containing from 2 to 4carbon atoms and, together with the nitrogen atom, morpholino,piperidino and piperazino, with the provisio that at least one of R¹, R²and R³ is other than hydroxygen,

(3) converting the aminated polymer to the salt form by a processselected from the group consisting of (a) acidifying with an acidselected from the group consisting of mineral acids andlow-molecular-weight carboxylic acids having from 1 to 7 carbon atoms,(b) quaternizing the tertiary aminated polymer by reaction with aquaternizing compound selected from the group consisting of3-chloro-2-hydroxypropyl trimethyl ammonium chloride, RCl, RBr and R²SO₄, wherein R is a member selected from the group consisting of methyland ethyl, and (c) quaternizing the tertiary aminated polymer byreaction with a quaternizing compound selected from the group consistingof ethylene oxide, propylene oxide, glycidol and glycidyl trimethylammonium chloride followed by acidifying with said acid of (a) above; aswell as a process for imparting an antistatic effect to hair whichcomprises applying to hair the above aqueous hair-treatment composition.

The cationic polymers suitable for use in accordance with the inventionand the processes by which they are produced are known.

Thus, the epoxidation of butadiene oligomers is described, for example,in Chemiker-Zeitung 95 (1971), No. 20, pages 857 to 863. The reaction ofepoxidized polybutadienes with tertiary amines to form quaternaryammonium polymers is known from published German patent application No.21 41 941 (and corresponding British publication No. 1,342,269). Thereaction of epoxidized butadiene homopolymers or copolymers with primaryand secondary aliphatic and cycloaliphatic amines is described inpublished German patent application No. 27 32 736 (and correspondingBritish publication No. 1,602,560). Conversion of the polymeric tertiaryamines, which are formed during the reaction of the polyepoxides withsecondary amines, into polymeric quaternary ammonium salts may also becarried out in known manner by alkylation with 3-chloro-2-hydroxypropyltrimethylammonium chloride, methyl chloride, ethyl chloride, dimethylsulfate, diethyl sulfate or by the addition of 1,2-monoepoxides, such asethylene oxide, propylene oxide, glycidol or glycidyl trimethylammoniumchloride.

Suitable starting products for producing the cationic polymers used inaccordance with the invention are 1,3-diene homopolymers or copolymers.Suitable 1,3-dienes are, above all, butadiene, 1,3-pentadiene, isopreneand chloroprene. Liquid butadiene homopolymers or copolymers arepreferably used. However, mono-olefins, such as ethylene, propylene,styrene, or acrylic acid derivatives may also be present as comonomers.The poly-1,3-dienes should contain at least 10 1,3-diene units permolecule. Liquid butadiene homopolymers are particularly suitable. Thedouble bonds present in poly-1,3-dienes of the type in question may havethe cis-configuration or trans-configuration or may be arranged in thevinyl position, depending on the polymerization conditions. It ispreferred to use polymers of which more than 50% show the1,4-cis-configuration at the double bonds.

The poly-1,3-dienes should be epoxidized to a conversion of at least 10%of the double bond present. Polyepoxides containing from 3 to 6% byweight of epoxide oxygen are particularly suitable.

Amines suitable for reaction with the polyepoxides are, for example,methylamine, ethylamine, isopropylamine, monoethanolamine,dimethylamine, diethylamine, diethanolamine, morpholine, piperidine,piperazine, trimethylamine, triethylamine, triethanolamine,N,N-dimethylethanolamine. The reaction products with dimethylamine andmorpholine are preferred.

The reaction with tertiary amines leads directly to polymeric quaternaryammonium compounds which are converted into the salt form by reactionwith mineral acids or with low molecular weight carboxylic acids,preferably having from 1 to 7 carbon atoms, such as acetic acid, lacticacid, glycolic acid. Conversion with hydrochloric acid into thehydrochlorides is preferred.

The reaction with primary and secondary amines leads to polymericsecondary and tertiary amines which, after conversion into the saltform, are suitable as cationic polymers for use in accordance with theinvention.

However, the polymeric tertiary amines obtained by reaction withsecondary amines may also be converted by alkylation into polymericquaternary ammonium compounds. It is preferred to convert reactionproducts of epoxidized poly-1,3-dienes with dimethylamine into polymericquaternary ammonium salts by alkylation with glycidyl trimethylammoniumchloride or with 3-chloro-2-hydroxypropyl trimethylammonium chloride.Another preferred group of cationic polymers for use in accordance withthe invention is obtained by reacting the poly-1,3-diene epoxides withdimethylamine and quaternizing the reaction products obtained by theaddition of ethylene oxide, followed by conversion into the salt form.

The use of the cationic polymers obtainable as described in accordancewith the invention in cosmetic hair treatment preparations providesthese preparations with a distinct antistatic effect when applied tohuman hair without any of the increased "heaviness" which normallyoccurs with cation-active compounds. By virtue of this effect, cosmetichair-treatment preparations of the type in question considerably improvethe set and body of the hair. This effect is surprising insofar as knowncationic polymers produce hardly any antistatic effects, particularlywhen applied from formulations containing anionic tensides.

Antistatic activity may be tested, for example, as follows:

Strands of hair approximately 20 cm long and weighing approximately 2 gare subjected to a single bleaching treatment and to a single cold-wavetreatment using standard commercial preparations (without the cationicpolymers used in accordance with the invention), washed, rinsed anddried. 0.5 ml of a test solution containing, for example, 1% by weightof the cationic polymer is applied by pipette to the strands of hairthus pretreated and rubbed in. Instead of using the test solution, it isalso possible to use any cosmetic hair-treatment preparation containingthe cationic polymers to be used in accordance with the invention. Afterthe treatment, the strands of hair are rinsed with clear, warm (35° C.)water, dried for 30 minutes at 60° C. and then conditioned for 24 hoursat 20° C./50% relative air humidity.

Thereafter, the strands of hair are combed 20 times using a hard rubbercomb. In the case of the untreated hair samples, this producesconsiderable static charging of the strands of hair, as reflected in adistinct spreading of the hair ends.

The strands of hair treated with the cationic polymers used inaccordance with the invention or with preparations containing them arenot statically charged and remain parallel after combing.

Cosmetic hair-treatment preparations suitable for use in accordance withthe invention are, for example, shampoos, hair after treatmentpreparations, for example hair rinses, hair care preparations, hairlotions, hair lacquers, hair sprays, hair dyes and hair wavingpreparations However, the products may also be used with advantage inbath additives, shower baths and liquid body shampoos because they arealso used for washing the hair or come into contact with the hair inuse.

The cationic polymers used in accordance with the invention areincorporated in the cosmetic hair-treatment preparations mentioned abovein quantities of from 0.1% to 10% by weight and preferably in quantitiesof from 0.5% to 5.0% by weight, based on the preparation as a whole orin the case of aerosol preparations, on the propellent-free activesolution.

The cationic polymers used in accordance with the invention areparticularly effective in cosmetic hair-treatment preparationscontaining anionic surface-active compounds, because an antistaticeffect would otherwise be impossible to obtain with preparations such asthese. Suitable anionic surface-active compounds are, for example,alkali metal, magnesium, ammonium and/or lower alkanol ammonium salts ofalkyl sulfuric acid half esters containing from 8 to 18 and preferablyfrom 12 to 16 carbon atoms in the alkyl (so-called alkyl sulfates) or ofalkyl polyethyleneglycol ether sulfuric acid half esters containing from8 to 18 and preferably from 12 to 16 carbon atoms in the alkyl and from1 to 6 ethylene-glycol ether groups in the molecule (so-called alkylether sulfates). Other suitable anionic surface-active compounds areprimary and secondary, linear alkane sulfonates containing from 10 to 18carbon atoms, alkene sulfonates containing from 10 to 18 carbon atomsand hydroxy alkane sulfonates containing from 10 to 18 carbon atoms, ofthe type obtained by sulfonating linear olefins containing from 10 to 18carbon atoms, higher fatty acid alkylol amide sulfates and higher fattyacid alkylol amide polyethyleneglycol ether sulfates, sulfated higherfatty acid monoglycerides, sulfosuccinic acid monoalkyl esterscontaining from 8 to 18 carbon atoms in the alkyl or dialkyl esterscontaining from 6 to 10 carbon atoms in the alkyls, alkylpolyethyleneglycol ether carboxylates containing from 8 to 18 carbonatoms in the alkyl and from 2 to 6 polyethyleneglycol ether groups inthe molecule, acyl sarcosines, acyl taurides and acyl isethionatecontaining from 8 to 18 carbon atoms in the acyl groups.

In addition to the anionic surface-active compounds, zwitterionic oramphoteric wash-active substances may be used in quantities of up toabout half the content of anionic surface-active compounds. Suitablezwitterionic wash-active substances are, for example, alkyl betaines,alkyl aminopropyl betaines, alkyl imidazolinium betaines, alkylamidocarboxylic acids, in each case containing from 8 to 18 carbon atomsin the alkyl. Examples of such suitable zwitterionic tensides arecocoalkyl dimethylaminoacetic acid, cocoalkylamidopropyldimethylaminoacetic acid or N-hydroxyethyl-N-coco-alkylamidoethylglycine.

The cationic polymers are preferably used in accordance with theinvention in a shampoo which, in addition to 0.5 to 5% by weight of thecationic polymer, contains from 5 to 30% by weight of alkylether sulfatetensides and from 1 to 5% by weight of a zwitterionic or amphotericwash-active substance.

In addition, refatting constituents, such as for example ethoxylatedhigher fatty acid partial glycerides or glycerol polyethyleneglycolether higher fatty acid esters, ethoxylated sorbitan higher fatty acidesters and also cosmetic oil components may be used in addition to theabove-mentioned components.

The cosmetic hair-treatment preparations may also contain non-ionic washactive substances and the usual additives and auxiliaries, activesubstances, solvents, propellent gases, thickeners, dyes, opacifiers,fragrances, preservatives, stabilizers and buffers appropriate to theparticular application or formulation.

The following Examples are intended to illustrate the invention withoutlimiting it in any way.

EXAMPLES (A) Preparation of the cationic polymers EXAMPLE 1

Epoxidation of Polybutadiene

In a glass apparatus consisting of a 4-liter three-necked flask, stirrerand intensive condenser, 540 g of a polybutadiene of which the viscosityat 20° C. according to DIN 53015 amounted to approximately 3 poises andthe iodine number (according to Wijs) amounted to approximately 450g/100 g and which predominantly contained 1,4-cis-double bonds (Polyolhuls® 130, a product of Chem. Werke Huls A.G., Germany) were dissolvedin 2000 ml of chloroform. 190 g of 40% peracetic acid (in glacial aceticacid) containing 19 g of dissolved sodium acetate were added dropwiseover a period of 7.5 hours with vigorous stirring to the solutionpreviously heated to 50° C. in such a way as to produce a steady, gentlereflux of the chloroform boiling under the effect of the heat ofreaction. Thereafter, the reaction mixture was stirred for another 2hours at 50° C. and then cooled to 30° C. The epoxide was precipitatedby pouring the reaction mixture into 12,000 ml of methanol undercontinuous stirring. The viscous oil, precipitating to the bottom of thecontainer, was separated off, mixed three times with 5 liters ofmethanol and separated and then washed until neutral. The oily reactionproduct was freed from volatile constituents in vacuo. The yieldamounted to 95% of the theoretical. The product contained 2.5% by weightof epoxide oxygen.

EXAMPLES 2 TO 8

Starting with 540 g of polybutadiene, epoxidation was carried out in thesame way as in Example 1 using the quantities of peracetic acid (40% inglacial acetic acid) shown in Table 1. The yields and epoxide oxygencontents indicated were obtained.

                  TABLE 1                                                         ______________________________________                                                              Yield                                                          Quantity of peracetic                                                                        [% of                                                   Example                                                                              acid (40% in glacial                                                                         the theo-                                                                              % Epoxide oxygen                               No.    acetic acid)   retical] [% by weight]                                  ______________________________________                                        1       190 g         95       2.5                                            2       285 g         93       3.6                                            3       380 g         88.5     4.7                                            4       570 g         83.7     6.7                                            5       665 g         64.3     7.4                                            6       950 g         79.0     9.3                                            7      1140 g         71.1     10.3                                           8      1425 g         47.5     5.8                                            ______________________________________                                    

EXAMPLE 9 Reaction of the epoxidized polybutadiene with dimethylamine

50 g of a 40% aqueous solution of dimethylamine were added to 50 g ofepoxidized polybutadiene (Example 1) dissolved in 600 g of dioxane andthe combined solutions introduced into an autoclave of V4A-steel. Afterpurging twice with nitrogen, the contents of the autoclave were stirredunder an initial pressure of 5 bars and at the same time heated to 200°C., producing a maximum pressure of 32 bars. After cooling to 20° C.,the autoclave was vented and opened and the reaction productprecipitated by pouring into 2.5 liters of distilled water. The isolatedreaction product was purified by dissolution in dioxane andprecipitation in water and, after drying, was characterized by the aminenumber. The reaction product had an amine number of 55.3. The yieldamounted to 60% of the theoretical.

EXAMPLES 10 TO 16

The reaction of the epoxidized polybutadienes (Examples 2 to 8) wascarried out in the same way as in Example 9 starting with 50 g of theepoxides in 600 ml of dioxane, the amines shown in Table 2 being used.Reaction products having the amine numbers indicated in Table 2 wereobtained.

                  TABLE 2                                                         ______________________________________                                                                  Reaction                                                                      product                                             Example                                                                              Epoxide   Amine used         amine                                     No.    used      Type          Quantity                                                                             number                                  ______________________________________                                         9     Example 1 dimethylamine*                                                                               50 g  55.3                                    10     Example 2 dimethylamine*                                                                               70 g  69.1                                    11     Example 5 dimethylamine*                                                                               90 g  134.8                                   12     Example 5 monoethanolamine                                                                             61 g  98.5                                    13     Example 6 dimethylamine*                                                                              120 g  107.8                                   14     Example 6 methylamine*  225 g  240.4                                   15     Example 8 dimethylamine*                                                                              105 g  168.2                                   16     Example 8 morpholine     81 g  153.8                                   ______________________________________                                         *40% aqueous solution                                                    

EXAMPLES 10A TO 16A Preparation of the hydrochlorides

The amine reaction products of Examples 9 to 16 were dissolved indioxane and an equivalent quantity of 18% aqueous hydrochloric acidcalculated from the amine number was added to the resulting solutions.The solvent was then removed by evaporation in vacuo.

EXAMPLE 17 Quaternization with glycidyl trimethylammonium chloride

10 g of the reaction product of Example 9 was dissolved in 100 ml ofdioxane, followed by the addition of 50 mg of KOH and mixing with 1.8 gof glycidyl trimethylammonium chloride (80%, moist). The reactionmixture was heated under reflux to boiling point over a period of 2hours and kept at that temperature for another 5 hours, during which itbecame slightly cloudy. The reaction mixture was then concentrated to avolume of 50 ml and precipitated by pouring into 250 ml of distilledwater. The substance precipitated was separated off and dried. The yieldamounted to 9.7 g (i.e. 82.2% of the theoretical).

Conversion into the hydrochloride was carried out as in Examples 9 to16.

EXAMPLES 18 and 19

The amine reaction products indicated in Table 3 were alkylated as inExample 17 with the indicated quantities of glycidyl trimethylammoniumchloride (GMAC) and the yields of the hydrochloride obtained areindicated.

                  TABLE 3                                                         ______________________________________                                               Amine                                                                  Example                                                                              reaction  GMAC,    Yield %  Cl.sup.(-)                                 No.    product   80%      of theoretical                                                                         (% by weight)                              ______________________________________                                        17     Example 9 1.8 g    82.2     0.48                                       18     Example 10                                                                              2.2 g    72.9     2.18                                       19     Example 11                                                                              4.4 g    55.6     0.36                                       ______________________________________                                    

EXAMPLE 20 Quaternization with ethylene oxide

20 g of the reaction product of Example 10 were dissolved in 400 ml ofanhydrous dioxane and 0.5 g of sodium methylate added to the resultingsolution. The solution was then transferred to an autoclave, followed bythe addition of 5.4 g of ethylene oxide (i.e. approximately 5 mols/molof amino groups). After heating to 70° C. the solution was stirred for 5hours at that temperature. In that time, the pressure which wasinitially 5 bars fell to 4.1 bars. After cooling, the reaction mixturewas concentrated to dryness under reduced pressure. An addition ofapproximately 1 mol of ethylene oxide per amino group is calculated fromthe yield of 21.1 g obtained.

The quaternization product was converted into the readily water-solublehydrochloride by dissolution in dioxane followed by the addition ofapproximately 5 g of 18% hydrochloric acid and concentration to dryness.

(B) Application Examples EXAMPLE 21

    ______________________________________                                        Hair Shampoo                                                                  ______________________________________                                        Fatty alcohol (C.sub.12-18) + 2 EO-                                                                 30%      by weight                                      sulfate, Na salt (28%)                                                        Cocoalkylamidopropyl betaine (30%)                                                                  15%      by weight                                      Cationic polymer of Example 10                                                                      2.0%     by weight                                      (hydrochloride)                                                               Formaldehyde (40%)    0.2%     by weight                                      Water, perfume oil, colorant                                                                        ad 100%  by weight                                      ______________________________________                                         EO = mols of ethylene oxide                                              

EXAMPLE 22

    ______________________________________                                        Hair rinse                                                                    ______________________________________                                        Cetyl alcohol        1.5%     by weight                                       "Lorol" C16, a product of E. I.                                               DuPont Corp., U.S.A.                                                          Glycerol mono-/distearate                                                                          1.5%     by weight                                       "Cutina" GMS, a product of Henkel                                             KGaA, F. R. Germany                                                           Cationic polymer of Example 16                                                                     1.5%     by weight                                       (hydrochloride)                                                               Cetyl trimethylammonium                                                                            2.0%     by weight                                       chloride (25%)                                                                Water, perfume oil, colorant                                                                       ad 100%  by weight                                       ______________________________________                                    

EXAMPLE 23

    ______________________________________                                        Hair dye (brown)                                                              ______________________________________                                        Tallow fatty alcohol                                                                              8.0%     by weight                                        Fatty alcohol (C.sub.12-18) + 2 EO-                                                               25.0%    by weight                                        sulfate, Na salt (28%)                                                        Cationic polymer of Example 18                                                                    3.0%     by weight                                        p-tolylene diamine  1.5%     by weight                                        2,4 diaminoanisole  0.04%    by weight                                        p-aminophenol       0.23%    by weight                                        Resorcinol          0.4%     by weight                                        Ammonia, 25%        4.5%     by weight                                        Water               ad 100%  by weight                                        ______________________________________                                    

The preceeding specific embodiments are illustrative of the practice ofthe invention. It is to be understood however that other expedientsknown to those skilled in the art or disclosed herein, may be employedwithout departing from the spirit of the invention or the scope of theappended claims.

We claim:
 1. An aqueous hair rinse antistatic composition consistingessentially of: a hair treatment substance and a cationic antistaticagent present in an antistatic effective amount, which agent is anepoxidized, aminated, 1,3-diene salt cationic polymer that is thereaction product of:(1) a 1,3-diene homopolymer or predominantly1,3-diene copolymer, having at least 10 1,3-diene units per molecule, inwhich at least 10% of the double bonds present have been epoxidized, andwhich contains about 3-6% by weight of epoxide oxygen; which has beenaminated with (2) amine of the formula R¹ NR² R³ wherein: R¹ is a C₁₋₄alkyl, or a C₂₋₄ hydroxyalkyl; and R² and R³ are the same or differentand are hydrogen, C₁₋₄ alkyl, or a C₂₋₄ hydroxyalkyl; or an amineselected from the group consisting of morpholine, piperidine, andpiperazine; and converted to a salt by (3) (a) reacting the aminatedepoxidized 1,3-diene polymer with an acid which is a C₁₋₇ carboxylicacid or a mineral acid; or (b) alkylating the aminated epoxidized1,3-diene polymer with 3-chloro-2-hydroxypropyl trimethyl ammoniumchloride or with RCl, RBr, or R² SO₄ wherein R is methyl or ethyl, toform a quarternary ammonium salt; or (c) quaternizing the aminatedepoxidized 1,3-diene polymer with ethylene oxide, propylene oxide,glycidol, or glycidyl trimethylammonium chloride; and then furtherreacting the resulting quaternary ammonium salt with an acid which is aC₁₋₇ carboxylic acid or a mineral acid.
 2. An aqueous hair raiseantistatic composition according to claim 1, wherein the -,3-dienehomopolymer or predominantly 1,3-diene copolymer is a homopolymer of1,3-butadiene, 1,3-pentadiene, isoprene, or chloroprene; or is acopolymer of two or more of 1,3-butadiene, 1,3-pentadiene, isoprene,chloroprene, ethylene, propylene, styrene, and an acrylic acidderivative.
 3. An aqueous hair rinse antistatic composition according toclaim 2, wherein more than 50% of the double bonds of the 1,3-dienehomopolymer or predominantly 1,3-diene copolymer are in a cis1,4-configuration
 4. An aqueous hair rinse antistatic compositionaccording to claim 2, wherein the 1,3-diene homopolymer or predominantly1,3-diene copolymer is a homopolymer or copolymer of butadiene and isliquid under ambient conditions.
 5. An aqueous hair rinse antistaticcomposition according to claim 4, wherein the homopolymer or copolymerof butadiene has a viscosity of about 3 poises at 20° C. when measuredby the method of DIN 53.015.
 6. An aqueous hair rinse antistaticcomposition according to claim 1, wherein epoxidation of the 1,3-dienehomopolymer or predominantly 1,3-diene copolymer is by reaction withperacetic acid.
 7. An aqueous hair rinse antistatic compositionaccording to claim 1, wherein the amine is methylamine, ethylamine,isopropylamine, ethanolamine, dimethylamine, diethylamine,diethanolamine, morpholine, piperidine, piperazine, trimethylamine,triethylamine, triethanolamine, or N,N-dimethylethanolamine.
 8. Anaqueous hair rinse antistatic composition according to claim 7, whereinthe amine is dimethylamine, ethanolamine, methyl amine, or morpholine.9. An aqueous hair rinse antistatic composition according to claim 1,wherein step (3)(a) or step (3)(c) is used and the acid is acetic acid,lactic acid, glycolic acid, or hydrochloric acid.
 10. An aqueous hairrinse antistatic composition according to claim 9, wherein step (3)(c)is used and the quaternizing is with ethylene oxide.
 11. An aqueous hairrinse antistatic composition according to claim 1, wherein:(A) the1,3-diene homopolymer or predominantly 1,3-diene copolymer is ahomopolymer of 1,3-butadiene, 1,3-pentadiene, isoprene, or chloroprene;or is a copolymer of two or more of 1,3-butadiene, 1,3-pentadiene,isoprene, chloroprene, ethylene, propylene, styrene, and an acrylic acidderivative; (B) the amine is methylamine, ethylamine, isopropylamine,ethanolamine, dimethylamine, diethylamine, diethanolamine, morpholine,piperidine, piperazine, trimethylamine, triethylamine, triethanolamine,or N,N-dimethylethanolamine; and (C) the acid is acetic acid, lacticacid, glycolic acid, or hydrochloric acid.
 12. An aqueous hair rinseantistatic composition according to claim 1, wherein:(A) the 1,3-dienehomopolymer or predominantly 1,3-diene copolymer is a homopolymer orcopolymer of butadiene that is liquid under ambient conditions, and morethan 50% of the double bonds of the homopolymer or copolymer ofbutadiene are in a cis 1,4-configuration; (B) the amine isdimethylamine, monoethylamine, methylamine, or morpholine; (C) the acidis hydrochloric acid; (D) the alkylating agent is3-chloro-2-hydroxyethyltrimethylammonium chloride; and (E) thequaternizing is with glycidyl trimethyl ammonium chloride.
 13. Anaqueous hair rinse antistatic composition according to claim 1,wherein:(A) the 1,3-diene homopolymer or predominantly 1,3-dienecopolymer is a homopolymer or copolymer of butadiene that is liquidunder ambient conditions, and more than 50% of the double bonds of thehomopolymer or copolymer of butadiene are in a cis 1,4-configuration;(B) the amine is morpholine; and (C) the aminated epoxidized 1,3-dienehomopolymer or copolymer of butadiene is reacted with hydrochloric acidto form a salt.
 14. An aqueous hair rinse antistatic compositionaccording to claim 1, wherein:(A) the 1,3-diene homopolymer orpredominantly 1,3-diene copolymer is a homopolymer or copolymer ofbutadiene that is liquid under ambient conditions, and more than 50% ofthe double bonds of the homopolymer or copolymer of butadiene are in acis 1,4-configuration; (B) the amine is morpholine; and (C) the aminatedepoxidized homopolymer or copolymer of butadiene is quaternized withglycidyl trimethylammonium chloride and is then further reacted withhydrochloric acid to form a water soluble salt.
 15. An aqueous hairrinse antistatic composition according to claim 1, wherein(A) the1,3-diene homopolymer or predominantly 1,3-diene copolymer is ahomopolymer or copolymer of butadiene that is liquid under ambientconditions, and more than 50% of the double bonds of the homopolymer orcopolymer of butadiene are in a cis 1,4-configuration; (B) the amine isdimethylamine; and (C) the aminated epoxidized homopolymer or copolymerof butadiene is alkylated with ethylene oxide and then further reactedwith hydrochloric acid to form a water soluble salt.
 16. An aqueous hairrinse antistatic composition according to claim 1, wherein the cationicantistatic agent is present in about 0.1 to about 10% by weight, basedon the total weight of the composition.
 17. An aqueous hair rinseantistatic composition according to claim 16, wherein the cationicantistatic agent is present in about 0.5 to about 5% by weight, based onthe total weight of the composition.
 18. A method for imparting anantistatic effect to hair, comprising rinsing the hair with a hair rinseeffective amount of a composition according to claim
 1. 19. A method forimparting an antistatic effect to hair, comprising rinsing the hair witha hair rinse effective amount of a composition according to claim 12.20. A method for imparting an antistatic effect to hair, comprisingrinsing the hair with a hair rinse effective amount of a compositionaccording to claim 13.